KR20110125269A - Process for producing monomer for fluorinated resist - Google Patents

Process for producing monomer for fluorinated resist Download PDF

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KR20110125269A
KR20110125269A KR1020117023757A KR20117023757A KR20110125269A KR 20110125269 A KR20110125269 A KR 20110125269A KR 1020117023757 A KR1020117023757 A KR 1020117023757A KR 20117023757 A KR20117023757 A KR 20117023757A KR 20110125269 A KR20110125269 A KR 20110125269A
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fluorine
acid
acrylic acid
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KR101212565B1 (en
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신야 아키바
료 나다노
유타카 가츠하라
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샌트랄 글래스 컴퍼니 리미티드
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/04—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0215—Sulfur-containing compounds
    • B01J31/0222—Sulfur-containing compounds comprising sulfonyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/62—Halogen-containing esters
    • C07C69/65—Halogen-containing esters of unsaturated acids
    • C07C69/653—Acrylic acid esters; Methacrylic acid esters; Haloacrylic acid esters; Halomethacrylic acid esters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/90—Catalytic systems characterized by the solvent or solvent system used
    • B01J2531/94—Fluorinated solvents
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • C07C2531/025—Sulfonic acids

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Abstract

본 발명에서는, 술포닐기를 가지는 특정한 산 촉매의 존재 하,

Figure pct00105
-치환 아크릴산을 함불소알켄에 직접 부가 반응시켜,
Figure pct00106
-치환 아크릴산 에스테르계의 함불소 레지스트용 모노머류를 제조한다. 특정한 산 촉매를 사용함으로써, 알켄의 이성화, 디올체의 생성,
Figure pct00107
-치환 아크릴산의 과부가 반응이 부반응으로서 진행되는 가운데, 목적으로 하는 함불소알켄과
Figure pct00108
-치환 아크릴산의 부가 반응을 효율적으로 진행시켜, 공업적 규모로
Figure pct00109
-치환 아크릴산 에스테르계의 함불소 레지스트용 모노머류를 제조할 수 있다.In the present invention, in the presence of a specific acid catalyst having a sulfonyl group,
Figure pct00105
-By directly adding the substituted acrylic acid to the fluorine-alkene,
Figure pct00106
-Substituted acrylic ester monomers for fluorine-containing resists are prepared. By using a specific acid catalyst, isomerization of alkenes, production of diol bodies,
Figure pct00107
While the addition reaction of substituted acrylic acid proceeds as a side reaction, the target fluorine-alkene and
Figure pct00108
-Advances the addition of substituted acrylic acid efficiently, on an industrial scale
Figure pct00109
-Monomers for fluorine-containing resists of substituted acrylic acid esters can be produced.

Description

함불소 레지스트용 모노머류의 제조 방법{PROCESS FOR PRODUCING MONOMER FOR FLUORINATED RESIST}Manufacturing method of monomers for fluorine-containing resists {PROCESS FOR PRODUCING MONOMER FOR FLUORINATED RESIST}

본 발명은, ArF 레이저용 차세대 포토레지스트에 대응하는 모노머로서 유용한 화합물인, 식 [3]으로 나타내는

Figure pct00001
-치환 아크릴산 에스테르계의 함불소 레지스트용 모노머류의 제조 방법에 관한 것이다.This invention is represented by Formula [3] which is a compound useful as a monomer corresponding to the next-generation photoresist for ArF lasers.
Figure pct00001
The present invention relates to a method for producing monomers for fluorine-containing resists of substituted acrylic acid esters.

[화학식 1][Formula 1]

Figure pct00002
Figure pct00002

식 중, R1은 수소 원자, 불소 원자 또는 탄소수 1∼6의 직쇄 혹은 분기쇄가 있는 알킬기를 나타내고, 당해 알킬기의 일부 또는 전부가 불소 원자에 의해 치환되어 있어도 된다.In formula, R <1> represents a hydrogen atom, a fluorine atom, or a C1-C6 linear or branched alkyl group, and one part or all part of the said alkyl group may be substituted by the fluorine atom.

본 발명의 목적 화합물인, 식 [3]으로 나타내는

Figure pct00003
-치환 아크릴산 에스테르류는, 함불소 레지스트용 모노머로서 유용한 화합물(특허문헌 1)로서, 일반적인 에스테르 화합물의 합성법에 의해 합성할 수 있다. 구체적으로는, (A)카르본산 할라이드와 알코올류의 반응, (B)카르본산 무수물과 알코올류 사이의 반응, (C)카르본산과 알코올류의 탈수 축합 반응, 및 (D)카르본산에스테르류와 알코올류의 에스테르 교환 반응 등의 방법을 들 수 있다. 예를 들어, 특허문헌 2에는, 노르보르나닐알코올과
Figure pct00004
-치환 아크릴산 클로라이드의 반응에 의해, 대응하는 노르보르나닐에스테르를 합성할 수 있는 것이 기재되어 있다. 특허문헌 3에는, 산 촉매 존재 하,
Figure pct00005
-치환 아크릴산 무수물과 알코올을 반응시켜 목적의 에스테르 화합물을 제조하는 방법이 개시되어, 양호한 선택성으로 반응이 진행되는 데다, 고체의 염이 석출되지 않기 때문에, 용매량을 삭감할 수 있어, 생산성을 향상시킬 수 있는 등의 기재가 있다. 비특허문헌 1에는, 아크릴산메틸의 시클로헥사놀과의 에스테르 교환 반응에 부여하여, 아크릴산시클로헥실을 합성할 수 있는 것이 기재되어 있다. 또한, 특허문헌 4 및 특허문헌 5에는,
Figure pct00006
-치환 아크릴산을 치환 노르보르넨에 직접 작용시키면, 효율적인 부가 반응이 진행되어, 목적으로 하는 노르보르넨계 에스테르류가 얻어지는 것이 개시되어 있다.It is represented by Formula [3] which is an objective compound of this invention.
Figure pct00003
-Substituted acrylic acid esters are compounds useful as monomers for fluorine-containing resists (Patent Document 1), and can be synthesized by the synthesis of general ester compounds. Specifically, (A) reaction of carboxylic acid halide and alcohol, (B) reaction between carboxylic anhydride and alcohol, (C) dehydration condensation reaction of carboxylic acid and alcohol, and (D) carboxylic acid ester And transesterification reaction of alcohols with alcohols. For example, Patent Document 2 discloses norbornanyl alcohol and
Figure pct00004
It has been described that by the reaction of substituted acrylic acid chlorides, the corresponding norbornanyl esters can be synthesized. In Patent Document 3, in the presence of an acid catalyst,
Figure pct00005
A method of producing a desired ester compound by reacting an acrylic acid anhydride with an alcohol is disclosed. Since the reaction proceeds with good selectivity and no salts of solid are precipitated, the amount of solvent can be reduced, thereby improving productivity. It can be described as such. Non-patent document 1 describes that it can be given to the transesterification reaction of methyl acrylate with cyclohexanol, and the cyclohexyl acrylate can be synthesize | combined. In addition, in patent document 4 and patent document 5,
Figure pct00006
It is disclosed that when the substituted acrylic acid is directly acted on the substituted norbornene, an efficient addition reaction proceeds to obtain the desired norbornene esters.

일본 공개특허공보 제2004-307447호Japanese Laid-Open Patent Publication No. 2004-307447 일본 공개특허공보 제2003-040840호Japanese Laid-Open Patent Publication No. 2003-040840 일본 공개특허공보 제2005-179348호Japanese Laid-Open Patent Publication No. 2005-179348 일본 공개특허공보 제2004-175740호Japanese Laid-Open Patent Publication No. 2004-175740 일본 공개특허공보 제2007-091634호Japanese Laid-Open Patent Publication No. 2007-091634

일본 화학회편, 「신(新) 실험 화학 강좌(제14권) 유기 화합물의 합성과 반응 [II]」, 마루젠 출판 주식회사, 1977년 12월, p.1018 Japanese Chemical Society, Synthesis and Reaction of New Experimental Chemistry Lecture (Vol. 14) Organic Compound [II], Maruzen Publishing Co., December 1977, p.1018

공업적 규모에서의 식 [3]의 에스테르 화합물의 제조에 있어서, 이하와 같은 문제점이 있다. 특허문헌 2의 방법에서는,

Figure pct00007
-치환 아크릴산 클로라이드를 반응 기질로서 사용하고 있다. 그러나, 이
Figure pct00008
-치환 아크릴산 클로라이드를 염화티오닐 등에 의한
Figure pct00009
-치환 아크릴산의 염소화로 합성하면, 산 무수물 등이 생성되기 때문에, 선택성·수율이 저하되고, 고가의
Figure pct00010
-치환 아크릴산을 사용하는 경우에는 비용적으로 불리하다. 특허문헌 3의 방법에서는, 원리적으로 생성물 1당량에 대하여 1당량의
Figure pct00011
-치환 아크릴산이 부생한다. 그 때문에, 고가의
Figure pct00012
-치환 아크릴산을 사용하는 경우에는 비용적으로 불리하고, 제품화에는
Figure pct00013
-치환 아크릴산의 제거도 필요하여, 반드시 효율적인 제조법은 아니다. 본 발명자들은,
Figure pct00014
-치환 아크릴산과 알코올의 탈수 축합 반응도 시도하였으나, 입체 장해가 큰
Figure pct00015
-치환 아크릴산과 알코올끼리의 반응에서는, 부반응이 진행되어, 양호한 결과가 얻어지지 않았다.In the production of the ester compound of the formula [3] on an industrial scale, there are the following problems. In the method of patent document 2,
Figure pct00007
Substituted acrylic acid chloride is used as the reaction substrate. However, this
Figure pct00008
-Substituted acrylic acid chloride by thionyl chloride or the like
Figure pct00009
When synthesized by chlorination of substituted acrylic acid, acid anhydride and the like are produced, so that selectivity and yield are lowered and expensive
Figure pct00010
It is disadvantageous in cost when using substituted acrylic acid. In the method of Patent Document 3, in principle, 1 equivalent of 1 equivalent of the product
Figure pct00011
-Substitute acrylic acid byproduct. Therefore, expensive
Figure pct00012
-It is disadvantageous in the case of using substituted acrylic acid,
Figure pct00013
-Removal of substituted acrylic acid is also necessary, and is not necessarily an efficient manufacturing method. The present inventors,
Figure pct00014
-Dehydration condensation reaction of substituted acrylic acid and alcohol was also attempted, but steric hindrance
Figure pct00015
-In reaction of substituted acrylic acid and alcohol, side reaction advanced and the favorable result was not obtained.

특허문헌 1∼3의 방법은 모두 알코올류를 반응 기질로서 사용하고 있다. 즉, 이들 방법을 본 발명의 화합물에 적용하기 위해서는, 스킴 1에 나타내는 바와 같이, 식 [1]의 함불소알켄(1,1,1-트리플루오로-2-(트리플루오로메틸)펜타-4-엔-2-올 ; 이하, BTHB로 약칭하는 경우도 있다)을, 하이드로보레이션, 에스테르 부가 반응-에스테르 가수분해 등의 방법을 이용하여 대응하는 함불소디올로 변환한 후, 당해 함불소디올과 아크릴산, 혹은 아크릴산 할라이드, 아크릴산 무수물, 아크릴산 에스테르 등을 반응시킬 필요가 있다.All the methods of patent documents 1-3 use alcohol as a reaction substrate. Namely, in order to apply these methods to the compound of the present invention, as shown in Scheme 1, fluorine-alkene (1,1,1-trifluoro-2- (trifluoromethyl) penta- of formula [1] 4-en-2-ol (hereinafter sometimes abbreviated as BTHB) is converted into the corresponding fluorine-containing diol using a method such as hydroboration, ester addition reaction-ester hydrolysis, and then the fluorine-containing It is necessary to react diol with acrylic acid or acrylic acid halide, acrylic acid anhydride, acrylic acid ester, and the like.

[화학식 2][Formula 2]

Figure pct00016
Figure pct00016

한편, 특허문헌 4∼5과 같이 함불소알켄(BTHB)에

Figure pct00017
-치환 아크릴산을 부가시키는 방법을 검토한 결과, 공정수가 적고, 반응 효율이 높기 때문에, 공업화용의 방법이지만, 당 조건으로는 함불소알켄의 말단 이중 결합 부위가 내부 이중 결합으로 이성화되기 쉽고(스킴 2, 참고예 1 참조), 이성화된 것은 반응성이 낮기 때문에, 선택적으로 반응을 진행시키기가 곤란한 것을 알 수 있었다.On the other hand, fluorine-alkene (BTHB) as in Patent Documents 4-5
Figure pct00017
-As a result of examining the method of adding substituted acrylic acid, since it has few processes and high reaction efficiency, it is a method for industrialization, but under these conditions, the terminal double bond site of a fluorine-alkene is easy to isomerize with an internal double bond (scheme). 2, reference example 1), since the isomerization is low in reactivity, it was found that it is difficult to advance the reaction selectively.

[화학식 3](3)

Figure pct00018
Figure pct00018

즉,

Figure pct00019
-치환 아크릴산의 함불소알켄에 대한 부가와 경쟁적으로 함불소알켄의 이성화가 진행되기 때문에, 이성화도 고려하면서 부가 반응을 행할 필요가 있다. 본 발명자들은, 산 촉매의 종류를 나눈 검토를 행하였는데, 산 촉매가 메탄술폰산이나 p-톨루엔술폰산인 경우에는, 이성화도 부가 반응도 진행되지 않는 것을 알 수 있었다(비교예 참조).In other words,
Figure pct00019
-Since isomerization of fluorine-alkene advances competitively with addition of substituted acrylic acid to fluorine-alkene, it is necessary to perform addition reaction in consideration of isomerization. The inventors conducted a study of dividing the types of acid catalysts. However, when the acid catalysts were methanesulfonic acid or p-toluenesulfonic acid, neither isomerization nor addition reaction proceeded (see Comparative Example).

또한, 추가 검토의 결과, 조건에 따라서는, BTHB의 가수분해가 일어나 함불소디올체(이후, 디올체, 또는 iso-BTHB라고 하는 경우가 있다)가 생성되는 경우가 있는 것이 밝혀졌다(스킴 3 참조).Further, as a result of further investigation, it was found that depending on the conditions, hydrolysis of BTHB may occur to produce fluorine-containing diols (hereinafter sometimes referred to as diols or iso-BTHB) (Scheme 3). Reference).

[화학식 4][Formula 4]

Figure pct00020
Figure pct00020

또한, 반응 시간과 함께 생성된

Figure pct00021
-치환 아크릴산 에스테르의 비닐에 대하여, 또 한 분자의
Figure pct00022
-치환 아크릴산이 부가된 과부가체를 생성하는 것도 밝혀졌다(이후, 이 반응을 과부가 반응, 이 반응으로 얻어진 생성물을 과부가체라고 하는 경우가 있다).In addition, generated with the reaction time
Figure pct00021
For vinyl of substituted acrylic esters,
Figure pct00022
It was also found to produce a superaddition to which -substituted acrylic acid was added.

상기한 바와 같이, 특허문헌 4∼5의 방법은, 산 존재 하에서,

Figure pct00023
-치환 아크릴산을, 함불소노르보르넨에 대하여 직접 작용시키는 것인데, 함불소알켄이 노르보르넨이었기 때문에 이성화를 고려할 필요가 없었다.As mentioned above, the method of patent documents 4-5, in presence of an acid,
Figure pct00023
-Substituted acrylic acid acts directly on fluorinated norbornene, which is not necessary to consider isomerization because fluorinated alkenes were norbornene.

본 발명은, 산 촉매 하,

Figure pct00024
-치환 아크릴산을 함불소알켄에 직접 부가시키는 에스테르계 함불소 레지스트용 모노머의 제조에 있어서, 함불소알켄의 이성화, 함불소알켄의 가수분해, 목적 생성물에 대한
Figure pct00025
-치환 아크릴산의 과부가 반응이 부반응으로서 진행되는 가운데, 함불소알켄과
Figure pct00026
-치환 아크릴산의 부가 반응을 효율적으로 진행시켜, 공업적 규모에서의
Figure pct00027
-치환 아크릴산 에스테르계의 함불소 레지스트용 모노머류의 제조를 실현하는 것을 목적으로 한다. 이들 문제점을 모두 해결하는 조건은, 선행 문헌에는 개시되어 있지 않다.The present invention, under an acid catalyst,
Figure pct00024
In the production of monomers for ester-based fluorine resists, in which substituted acrylic acid is added directly to fluorine-alkenes, isomerization of fluorine-alkenes, hydrolysis of fluorine-alkenes, and target products
Figure pct00025
Fluorinated alkene and fluorinated alkenes
Figure pct00026
-The addition reaction of substituted acrylic acid is advanced efficiently, and on the industrial scale
Figure pct00027
It aims at realizing manufacture of monomers for fluorine-containing resists of substituted acrylic esters. The conditions for solving all these problems are not disclosed in the prior literature.

본 발명자들은 이러한 종래 기술의 문제점을 감안하여, 공업적 규모에서의 제조에 적합한 함불소 레지스트용 모노머류의 제조법을 확립하기 위해, 예의 검토를 행하였다. 그 결과, 함불소알켄과

Figure pct00028
-치환 아크릴산을 반응시킬 때에, 산 촉매로서 술포닐기를 가지는 특정한 산을 사용함으로써, 양호한 수율로 목적으로 하는 함불소 레지스트용 모노머류가 얻어지는 것을 알아내어, 본 발명의 완성에 도달하였다. 이 반응 과정에 있어서, 함불소알켄의 이성화, 디올체의 생성, 목적 생성물에 대한
Figure pct00029
-치환 아크릴산의 과부가 반응과 같은 부반응을 억제하면서, 목적으로 하는 부가 반응을 효율적으로 진행시키는 것은 특필해야 하는 것이다.MEANS TO SOLVE THE PROBLEM The present inventors earnestly examined in order to establish the manufacturing method of the monomers for fluorine-containing resists suitable for manufacture on an industrial scale in view of such a problem of the prior art. As a result, fluorine-alkenes and
Figure pct00028
When reacting substituted acrylic acid, it was found out that monomers for fluorine-containing resists can be obtained in a good yield by using a specific acid having a sulfonyl group as an acid catalyst, thereby reaching the completion of the present invention. In the course of this reaction, isomerization of fluorinated alkenes, formation of diol bodies,
Figure pct00029
-It is necessary to mention specially to advance the target addition reaction efficiently, suppressing side reactions, such as the addition reaction of substituted acrylic acid.

본 발명의 반응을 스킴 4에 나타낸다.The reaction of the present invention is shown in Scheme 4.

[화학식 5][Chemical Formula 5]

Figure pct00030
Figure pct00030

바꿔 말하면, 본 발명의 특징은 하기와 같다.In other words, the features of the present invention are as follows.

[발명 1][Invention 1]

식 [1]로 나타내는 함불소알켄과 식 [2]로 나타내는

Figure pct00031
-치환 아크릴산을 산 촉매의 존재 하에서 반응시키는, 식 [3]으로 나타내는 함불소 레지스트용 모노머류의 제조 방법에 있어서, 산 촉매가 식 [4]로 나타내는 술포닐기를 가지는 산인 것을 특징으로 하는 함불소 레지스트용 모노머류의 제조 방법.Fluorinated alkene represented by Formula [1] and represented by Formula [2]
Figure pct00031
In the method for producing monomers for fluorine-containing resists represented by formula [3], wherein the substituted acrylic acid is reacted in the presence of an acid catalyst, the acid catalyst is an acid having a sulfonyl group represented by formula [4]. The manufacturing method of the monomers for resists.

[화학식 6][Formula 6]

Figure pct00032
Figure pct00032

[화학식 7][Formula 7]

Figure pct00033
Figure pct00033

[R1은 수소 원자, 불소 원자 또는 탄소수 1∼6의 직쇄 혹은 분기쇄가 있는 알킬기를 나타내고, 당해 알킬기의 일부 또는 전부가 불소 원자에 의해 치환되어 있어도 된다.][R 1 represents a hydrogen atom, a fluorine atom or a linear or branched alkyl group having 1 to 6 carbon atoms, and part or all of the alkyl group may be substituted with a fluorine atom.]

[화학식 8][Formula 8]

Figure pct00034
Figure pct00034

[R1은 식 [2]와 동일하다.][R 1 is the same as Equation [2].]

[화학식 9][Formula 9]

Figure pct00035
Figure pct00035

[A는 산소 원자 또는 탄소 원자를 나타내고, Rf는 서로 각각 독립적으로 동일하거나 다른 불소 원자, 하이드록실기 또는 탄소수 1∼6의 함불소알킬기를 나타내며, n은 1 또는 3의 정수를 나타낸다.][A represents an oxygen atom or a carbon atom, R f each independently represents the same or different fluorine atom, hydroxyl group or C1-6 fluorine-containing alkyl group, n represents an integer of 1 or 3.]

[발명 2][Invention 2]

산 촉매의 pKa가 -5 이하인, 발명 1에 기재된 함불소 레지스트용 모노머류의 제조 방법.The manufacturing method of the monomer for fluorine-containing resists of invention 1 whose pKa of an acid catalyst is -5 or less.

[발명 3][Invention 3]

반응 온도가 30℃ 내지 200℃인, 발명 1 또는 2에 기재된 함불소 레지스트용 모노머류의 제조 방법.The manufacturing method of the monomer for fluorine-containing resists of invention 1 or 2 whose reaction temperature is 30 degreeC-200 degreeC.

[발명 4][Invention 4]

식 [2]로 나타내는

Figure pct00036
-치환 아크릴산 1몰에 대하여, 식 [1]로 나타내는 함불소알켄의 사용량이 2∼10몰인 것을 특징으로 하는, 발명 1 내지 3 중 어느 하나에 기재된 함불소 레지스트용 모노머류의 제조 방법.Represented by formula [2]
Figure pct00036
-The use amount of the fluorine-alkene represented by Formula [1] is 2-10 mol with respect to 1 mol of substituted acrylic acid, The manufacturing method of the monomer for fluorine-containing resists in any one of inventions 1-3 characterized by the above-mentioned.

본 발명에 의하면,

Figure pct00037
-치환 아크릴산의 함불소알켄에 대한 직접 부가에 있어서, 알켄의 이성화, 디올체의 생성, 과부가 반응이 부반응으로서 진행되는 가운데, 목적으로 하는 부가 반응을 효율적으로 진행시켜, 공업적 규모로
Figure pct00038
-치환 아크릴산 에스테르계의 함불소 레지스트용 모노머류를 제조할 수 있다. 또한,
Figure pct00039
-치환 아크릴산으로부터 1단계의 반응으로 목적으로 하는 함불소 레지스트용 모노머류를 효율적으로 공업적 규모로 제조할 수 있는 데다, 산 클로라이드나 산 무수물을 거치지 않고 제조할 수 있기 때문에, 특히 고가의
Figure pct00040
-치환 아크릴산을 사용하는 경우에는, 비용적으로도 우수하다. 제조된 함불소 레지스트용 모노머는, ArF 레이저용 차세대 포토레지스트에 대응하는 모노머로서 유용하다.According to the invention,
Figure pct00037
In the direct addition of substituted acrylic acid to the fluorine-alkene, while the isomerization of the alkene, the formation of the diol body, and the addition reaction proceed as side reactions, the target addition reaction can be efficiently carried out on an industrial scale.
Figure pct00038
-Monomers for fluorine-containing resists of substituted acrylic acid esters can be produced. Also,
Figure pct00039
-The monomers for fluorine-containing resists can be efficiently produced on an industrial scale by one-step reaction from substituted acrylic acid, and can be produced without going through an acid chloride or an acid anhydride.
Figure pct00040
-When substituted acrylic acid is used, it is excellent also in cost. The produced monomer for fluorine-containing resist is useful as a monomer corresponding to the next generation photoresist for ArF laser.

이하, 본 발명에 대해, 더욱 상세하게 설명한다.EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

본 발명은, 상기 스킴 4에 나타내는 바와 같이, 특정한 산 촉매의 존재 하, 식 [1]의 함불소알켄에 식 [2]의

Figure pct00041
-치환 아크릴산을 직접 부가하여, 식 [3]의
Figure pct00042
-치환 아크릴산 에스테르계의 함불소 레지스트용 모노머류를 제조하는 방법을 제공하는 것이다.As shown in Scheme 4, the present invention relates to a fluorine alkene of formula [1] in formula [2] in the presence of a specific acid catalyst.
Figure pct00041
-By directly adding substituted acrylic acid,
Figure pct00042
It provides a method for producing monomers for fluorine-containing resists of substituted acrylic esters.

산 촉매의 존재 하에서의 함불소알켄(BTHB)과

Figure pct00043
-치환 아크릴산의 부가 반응에는 이하와 같은 문제점이 있다.Fluorine-alkene (BTHB) in the presence of an acid catalyst
Figure pct00043
The addition reaction of -substituted acrylic acid has the following problems.

(1) 산 촉매에 따라서는, 함불소알켄의 말단 이중 결합 부위가 내부 이중 결합으로 이성화되기 쉽다. 내부 이중 결합은 말단 이중 결합에 비하여 반응성이 낮으므로, 이성체의 부가 반응의 선택성이 저하된다.(1) Depending on the acid catalyst, the terminal double bond sites of the fluorine-alkene are likely to be isomerized to internal double bonds. Since internal double bonds are less reactive than terminal double bonds, the selectivity of addition reaction of isomers is reduced.

(2) BTHB와 계내의 물이 반응하여 디올체가 생성됨으로써, 목적물에 대한 선택률이 저하됨과 함께 분리에 부하가 걸린다.(2) When BTHB reacts with water in the system to generate a diol body, the selectivity for the target product is lowered and a separation is applied.

(3) 반응 시간과 함께, 목적물 생성물의

Figure pct00044
-치환 아크릴산 부위의 비닐에 대하여, 또 한 분자의
Figure pct00045
-치환 아크릴산이 부가된 과부가체가 생성된다.(3) with the reaction time of the desired product
Figure pct00044
For the vinyl of the substituted acrylic acid moiety,
Figure pct00045
-A hyperaddition with addition of substituted acrylic acid is produced.

이들의 반응을 스킴 5에 정리한다.These reactions are summarized in Scheme 5.

[화학식 10][Formula 10]

Figure pct00046
Figure pct00046

스킴 5에 있어서,

Figure pct00047
-치환 아크릴산의 함불소알켄(BTHB)에 대한 부가 반응의 속도 정수를 k1로 하고,
Figure pct00048
-치환 아크릴산의 목적 생성물에 대한 과부가 반응의 속도 정수를 k2로 하고, BTHB로부터 BTHB 이성체로의 이성화의 속도 정수를 k3, BTHB의 가수분해에 의한 디올체 생성의 속도 정수를 k4로 하였을 때, BTHB의 이성화 및 가수분해를 억제하여, 효율적으로 목적 생성물로 변환하기 위해서는, 일반적으로는, k1[
Figure pct00049
-치환 아크릴산] > k3 또는, k1[
Figure pct00050
-치환 아크릴산] > k4가 되도록 [
Figure pct00051
-치환 아크릴산]의 농도가 높아지도록 설정하는 것이 유효하지만, 본 반응에서는, 과부가체가 생성되기 때문에, [
Figure pct00052
-치환 아크릴산]의 농도를 높게 하면, 최종적으로 과부가체가 증가하여 바람직하지 않다. 따라서, [
Figure pct00053
-치환 아크릴산]의 농도가 낮은 조건 하에서, k1 > k3 또는 k1 > k4가 되는 산 촉매가 있으면 유효하다. 이상적으로는, k1 >> k3 또는 k1 >> k4가 되는 산 촉매가 바람직하지만, 전술한 바와 같이 부가 반응을 진행시키는 산 촉매는 이성화 등의 부반응도 진행시킨다.In scheme 5,
Figure pct00047
The rate constant of the addition reaction of the substituted acrylic acid to the fluorine-alkene (BTHB) is k 1 ,
Figure pct00048
- the isomerization rate constant of a BTHB isomer from substituted widow for a desired product of acrylic acid is, and the rate constant of the reaction with k 2, BTHB the rate constant of the diol body produced by the hydrolysis of k 3, BTHB to k 4 In order to suppress isomerization and hydrolysis of BTHB and efficiently convert it into a desired product, k 1 [
Figure pct00049
-Substituted acrylic acid]> k 3 or, k 1 [
Figure pct00050
-Substituted acrylic acid]> k 4 such that
Figure pct00051
-Substituted acrylic acid] is effective to set the concentration higher, but in this reaction, since a hyperaddition is produced, [
Figure pct00052
-Substituted acrylic acid], it is not preferable to increase the excess value finally. therefore, [
Figure pct00053
-Substituted acrylic acid] is effective if there is an acid catalyst such that k 1 > k 3 or k 1 > k 4 . Ideally, an acid catalyst of k 1 >> k 3 or k 1 >> k 4 is preferable, but as described above, the acid catalyst for advancing the addition reaction also advances side reactions such as isomerization.

본 발명의 제조 방법은, 알켄과 아크릴산의 부가 반응에 있어서, 알켄의 이성화, 디올체의 생성, 아크릴산의 과부가 반응이 진행되는 가운데, 목적으로 하는 반응을 효율적으로 진행시키는 산 촉매 및 바람직한 반응 조건을 특정한 것이다. 또한, 본 발명의 제조 방법은, 배치식(batch type) 반응 장치에서 실시할 수 있다. 이하에서 그 반응 조건을 구체적으로 서술하는데, 각각의 반응 장치에 있어서, 당업자가 용이하게 조절할 수 있을 정도의 반응 조건의 변경을 방해하는 것은 아니다.In the production method of the present invention, in the addition reaction of alkene and acrylic acid, an isomerization of an alkene, formation of a diol body, and an addition reaction of acrylic acid proceed with an acid catalyst and a preferable reaction condition for efficiently carrying out the target reaction. Is specific. In addition, the manufacturing method of this invention can be implemented in a batch type reaction apparatus. Although the reaction conditions are described concretely below, in each reaction apparatus, it does not prevent the change of reaction conditions to the extent that a person skilled in the art can easily adjust.

본 발명에서 원료로서 사용되는 식 [1]의 함불소알켄(1,1,1-트리플루오로-2-(트리플루오로메틸)펜타-4-엔-2-올)은 공지된 방법으로 합성할 수 있고, 예를 들어, 헥사플루오로아세톤과 프로필렌을 활성탄의 존재 하, 접촉 기상 반응시킴으로써 제조할 수 있다(일본 공개특허공보 평5-155795호).Fluoroalkene (1,1,1-trifluoro-2- (trifluoromethyl) penta-4-en-2-ol) of formula [1] to be used as a raw material in the present invention was synthesized by a known method. For example, hexafluoroacetone and propylene can be produced by contact gas phase reaction in the presence of activated carbon (JP-A-5-155795).

본 발명에서 원료로서 사용되는 식 [2]의

Figure pct00054
-치환 아크릴산의 치환기 R1은 수소 원자, 불소 원자 또는 탄소수 1∼6의 직쇄 혹은 분기쇄가 있는 알킬기를 나타내고, 당해 알킬기의 일부 또는 전부가 불소 원자에 의해 치환되어 있어도 된다. R1의 구체예로는, 메틸기, 에틸기, n-프로필기, iso-프로필기, n-부틸기, iso-부틸기, t-부틸기, 불소 원자, 트리플루오로메틸기(CF3-), 펜타플루오로에틸기(C2F5-), CF3CH2-, CF3(CF3)CH- 등을 들 수 있다. 이들 중, 반응성의 관계에서, 산성도가 강한 산이 바람직하고, 불소 원자, 불소 치환된 알킬기가 바람직하게 사용된다. 또한, 원료 입수의 관계 혹은 다른 범용 모노머와의 중합성의 관계에서, R1은 수소 원자, 메틸기 또는 트리플루오로메틸기가 바람직하다.Of formula [2] used as a raw material in the present invention
Figure pct00054
Substituent R <1> of -substituted acrylic acid represents a hydrogen atom, a fluorine atom, or a C1-C6 linear or branched alkyl group, and one part or all part of the said alkyl group may be substituted by the fluorine atom. Specific examples of R 1 include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, t-butyl group, fluorine atom, trifluoromethyl group (CF 3- ), Pentafluoroethyl group (C 2 F 5- ), CF 3 CH 2- , CF 3 (CF 3 ) CH- and the like. Among these, in the relationship of reactivity, the acid with strong acidity is preferable, and a fluorine atom and a fluorine-substituted alkyl group are used preferably. In addition, R 1 is preferably a hydrogen atom, a methyl group or a trifluoromethyl group in terms of raw material availability or polymerizable relationship with other general purpose monomers.

이들

Figure pct00055
-치환 아크릴산은 공지된 방법으로 합성할 수 있다. R1이 수소, 메틸기, 할로겐 등인 경우에는 시약으로서도 용이하게 입수 가능하다. 또한, 예를 들어 R1이 트리플루오로메틸기인 경우에는 2-브로모-3,3,3-트리플루오로프로펜에 대하여 Pd를 촉매로 하는 CO 삽입 반응을 행함으로써(Heck 반응), 용이하게 합성할 수 있는 것이 알려져 있다(일본 공개특허공보 소59-21648호).these
Figure pct00055
Substituted acrylic acid can be synthesized by a known method. When R <1> is hydrogen, a methyl group, a halogen, etc., it is easily obtainable also as a reagent. For example, when R 1 is a trifluoromethyl group, CO insertion reaction using Pd as a catalyst for 2-bromo-3,3,3-trifluoropropene is easily performed (Heck reaction). It is known that it can be synthesize | combined easily (JP-A-59-21648).

본 발명의 함불소알켄 [1]과

Figure pct00056
-치환 아크릴산 [2]의 부가 반응에 있어서의 산 촉매로는, 식 [4]로 나타내는 술포닐기를 가지는 산이 바람직하게 사용된다.Fluorine-alkene [1] of the present invention
Figure pct00056
As the acid catalyst in the addition reaction of -substituted acrylic acid [2], an acid having a sulfonyl group represented by Formula [4] is preferably used.

[화학식 11][Formula 11]

Figure pct00057
Figure pct00057

[A는 산소 원자 또는 탄소 원자를 나타내고, Rf는 서로 각각 독립적으로 동일하거나 다른 불소 원자, 하이드록실기 또는 탄소수 1∼6의 함불소알킬기를 나타내며, n은 1 또는 3의 정수를 나타낸다.][A represents an oxygen atom or a carbon atom, R f each independently represents the same or different fluorine atom, hydroxyl group or C1-6 fluorine-containing alkyl group, n represents an integer of 1 or 3.]

식 [4]의 산은, A가 산소 원자인 경우에는 식 [5]로 나타낼 수도 있고, A가 탄소 원자인 경우에는 식 [6]으로 나타낼 수도 있다.The acid of Formula [4] may be represented by Formula [5] when A is an oxygen atom, and may be represented by Formula [6] when A is a carbon atom.

[화학식 12][Chemical Formula 12]

Figure pct00058
Figure pct00058

[Rf는 식 [4]와 동일하다.][R f is the same as Equation [4].

[화학식 13][Formula 13]

Figure pct00059
Figure pct00059

[Rf는 식 [4]와 동일하다.][R f is the same as Equation [4].

Rf의 함불소알킬기로는, 트리플루오로메틸기(CF3-), 펜타플루오로에틸기(C2F5-), CF3CH2-, CF3(CF3)CH-, C3F7-, CF3(CF2)CH2- 및 노나플루오로부틸기(C4F9-)를 들 수 있지만, 바람직하게는, 트리플루오로메틸기(CF3-), 펜타플루오로에틸기(C2F5-), 노나플루오로부틸기(C4F9-) 등의 퍼플루오로알킬기, 더욱 바람직하게는, 입수의 관계에서 트리플루오로메틸기(CF3-)가 좋다. Examples of the fluorine-containing alkyl group for R f include a trifluoromethyl group (CF 3- ), a pentafluoroethyl group (C 2 F 5- ), CF 3 CH 2- , CF 3 (CF 3 ) CH-, and C 3 F 7 -CF 3 (CF 2 ) CH 2 -and nonafluorobutyl group (C 4 F 9- ), but preferably, trifluoromethyl group (CF 3- ), pentafluoroethyl group (C 2 F 5-good)), such as perfluoro-alkyl group, more preferably, a methyl group (CF 3 trifluoromethyl in relation to the available-), nona-butyl group (C 4 F 9 fluoro.

따라서, 식 [4]로 나타내는 술포닐기를 가지는 산으로는, 플루오로황산, 황산, 트리플루오로메탄술폰산, 노나플루오로부탄술폰산, 트리스(트리플루오로메탄술포닐)메탄 등을 들 수 있지만, 입수의 관계에서, 황산, 트리플루오로메탄술폰산, 트리스(트리플루오로메탄술포닐)메탄이 바람직하다. 그 중에서도 트리스(트리플루오로메탄술포닐)메탄이 특히 바람직하다.Therefore, examples of the acid having a sulfonyl group represented by the formula [4] include fluorosulfuric acid, sulfuric acid, trifluoromethanesulfonic acid, nonafluorobutanesulfonic acid, tris (trifluoromethanesulfonyl) methane, and the like. In terms of availability, sulfuric acid, trifluoromethanesulfonic acid and tris (trifluoromethanesulfonyl) methane are preferred. Especially, tris (trifluoromethanesulfonyl) methane is especially preferable.

또한, 식 [4]로 나타내는 술포닐기를 가지는 산의 pKa는 -5 이하인 것이 바람직하지만, -12 이하가 보다 바람직하고, -17 이하가 특히 바람직하다. pKa가 -5보다 큰 경우에는, 부가 반응이 진행되지 않거나 매우 느린 것으로서, 바람직하지 않다. pKa의 하한은, 부가 반응이 진행되는 한에 있어서는 특별히 한정되지 않지만, 당해 술포닐기를 가지는 산은 산이기 때문에, 당해 산을 문제없이 제조할 수 있고, 또한 문제없이 취급할 수 있을 정도이면 사용할 수 있다.Moreover, although it is preferable that pKa of the acid which has a sulfonyl group represented by Formula [4] is -5 or less, -12 or less are more preferable, and -17 or less are especially preferable. If pKa is greater than -5, the addition reaction does not proceed or is very slow, which is undesirable. The lower limit of the pKa is not particularly limited as long as the addition reaction proceeds. However, since the acid having the sulfonyl group is an acid, the acid can be produced without problems and can be used as long as it can be handled without problems. .

본 반응에 사용하는 산 촉매의 양은, 함불소알켄,

Figure pct00060
-치환 아크릴산, 용매 및 산의 종류의 조합에 의해 촉매로서의 효과가 변동되기 때문에, 일의적으로는 결정할 수 없지만, 기질의
Figure pct00061
-치환 아크릴산 1몰에 대하여 0.0001∼1몰이고, 0.005∼0.5몰이 바람직하고, 0.01∼0.2몰이 보다 바람직하다. 기질의
Figure pct00062
-치환 아크릴산 1몰에 대하여 산 촉매가 0.0001보다 적으면, 산을 첨가하는 효과가 없기 때문에, 바람직하지 않다. 또한, 기질의
Figure pct00063
-치환 아크릴산 1몰에 대하여 산 촉매가 1몰을 초과하면 경제적으로 바람직하지 않다.The amount of acid catalyst used in this reaction is fluorine-alkene,
Figure pct00060
-The effect as a catalyst varies depending on the combination of substituted acrylic acid, a solvent and an acid, so it cannot be determined uniquely, but
Figure pct00061
It is 0.0001-1 mol with respect to 1 mol of substituted acrylic acid, 0.005-0.5 mol is preferable, and its 0.01-0.2 mol is more preferable. Temperamental
Figure pct00062
If the acid catalyst is less than 0.0001 per 1 mole of substituted acrylic acid, it is not preferable because there is no effect of adding an acid. Also, of the substrate
Figure pct00063
It is economically undesirable if the acid catalyst exceeds 1 mole with respect to 1 mole of substituted acrylic acid.

본 반응에 있어서의

Figure pct00064
-치환 아크릴산과 함불소알켄의 혼합비는,
Figure pct00065
-치환 아크릴산 1몰에 대하여 2∼10몰이고, 3∼6몰이 바람직하고 3.5∼5몰이 특히 바람직하다.
Figure pct00066
-치환 아크릴산 1몰에 대하여 함불소알켄이 1몰 미만에서는, 함불소알켄의 이성화에 수반하여 반응의 선택률, 목적물의 수율 모두 저하되는 것 외에, 상대적으로
Figure pct00067
-치환 아크릴산이 많아지기 때문에 과부가체의 생성이 촉진되므로 바람직하지 않다. 한편, 함불소알켄이 10몰을 초과하면 경제적으로 불필요하다.In this reaction
Figure pct00064
The mixing ratio of substituted acrylic acid and fluorine-alkene is
Figure pct00065
-It is 2-10 mol with respect to 1 mol of substituted acrylic acid, 3-6 mol is preferable, and 3.5-5 mol is especially preferable.
Figure pct00066
When the fluorine-alkene is less than 1 mole with respect to 1 mole of substituted acrylic acid, both the selectivity of the reaction and the yield of the target product are lowered with the isomerization of the fluorine-alkene.
Figure pct00067
It is not preferable because the production of the hyperaddition is promoted because of the increase of substituted acrylic acid. On the other hand, when the fluorine-alkene exceeds 10 mol, it is economically unnecessary.

본 반응은 용매의 비존재 하에서도 진행되는데, 용매를 공존시켜 반응을 행해도 된다. 이러한 용매로는, 아세토니트릴, 벤조니트릴 등의 니트릴계 용매, N,N-디메틸포름아미드, N,N-디메틸아세트아미드, N,N-디메틸이미다졸리디논 등의 아미드계 용매, 디메틸술폭시드 등의 술폭시드계 용매, 디에틸에테르, 디이소프로필에테르, 디부틸에테르 등의 에테르계 용매, 염화메틸렌, 클로로포름, 4염화탄소 등의 할로겐화 용매, 벤젠, 톨루엔, 크실렌 등의 방향족계 탄화수소 용매, 펜탄, 헥산, 헵탄 등의 지방족 탄화수소 용매에서 선택되는 적어도 1종의 화합물이 바람직하고, 이들은 단독으로 사용해도 되고, 복수의 용매를 병용해도 된다.Although this reaction advances even in absence of a solvent, you may react by coexisting a solvent. Examples of such a solvent include nitrile solvents such as acetonitrile and benzonitrile, amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, and N, N-dimethylimidazolidinone, and dimethyl sulfoxide. Sulfoxide solvents, ether solvents such as diethyl ether, diisopropyl ether and dibutyl ether, halogenated solvents such as methylene chloride, chloroform and carbon tetrachloride, aromatic hydrocarbon solvents such as benzene, toluene and xylene, At least 1 type of compound chosen from aliphatic hydrocarbon solvents, such as a pentane, hexane, and heptane, is preferable, These may be used independently and may use several solvent together.

용매를 사용하는 경우, 용매의 사용량은,

Figure pct00068
-치환 아크릴산 1g에 대하여 0.01∼100g이고, 1∼30g이 바람직하고, 2∼10g이 보다 바람직하다. 용매량이
Figure pct00069
-치환 아크릴산 1g에 대하여 100g을 초과하면 후처리 및 회수 등의 수고로부터 경제적으로 바람직하지 않다.When using a solvent, the amount of solvent used is
Figure pct00068
It is 0.01-100 g with respect to 1 g of substituted acrylic acid, 1-30 g is preferable, and its 2-10 g is more preferable. Amount of solvent
Figure pct00069
If it exceeds 100 g with respect to 1 g of substituted acrylic acid, it is economically unfavorable from the trouble of post-treatment and recovery.

본 반응에 있어서, 반응 온도는 30∼200℃이고, 50∼150℃가 바람직하고, 80℃∼130℃가 보다 바람직하다. 30℃ 미만에서는 반응 속도가 매우 느려 실용적 제조법으로는 되지 않는다. 또한, 200℃를 초과하면

Figure pct00070
-치환 아크릴산이 중합하기 때문에 바람직하지 않다.In this reaction, reaction temperature is 30-200 degreeC, 50-150 degreeC is preferable and 80 degreeC-130 degreeC is more preferable. If it is less than 30 degreeC, reaction rate is very slow and it does not become a practical manufacturing method. In addition, when it exceeds 200 degreeC
Figure pct00070
It is not preferable because substituted acrylic acid polymerizes.

또한, 본 반응에 있어서,

Figure pct00071
-치환 아크릴산 혹은 생성물의 함불소 레지스트용 모노머류가 중합하는 것을 방지하는 것을 목적으로 하여 중합 금지제를 공존시켜도 된다. 사용하는 중합 금지제는 메토퀴논, 2,5-디-t-부틸하이드로퀴논, 1,2,4-트리하이드록시벤젠, 2,5-비스테트라메틸부틸하이드로퀴논, 류코퀴니자린, 논플렉스 F, 논플렉스 H, 논플렉스 DCD, 논플렉스 MBP, 오조논 35, 페노티아진, 테트라에틸티우람디술파이드, 1,1-디페닐-2-피크릴히드라질, 1,1-디페닐-2-피크릴히드라진, Q-1300, Q-1301, 2-메톡시페노티아진에서 선택되는 적어도 1종의 화합물인 것이 바람직하다. 상기 중합 금지제는 시판품으로서 용이하게 입수 가능하다.In addition, in this reaction,
Figure pct00071
A polymerization inhibitor may coexist for the purpose of preventing the polymerization of -substituted acrylic acid or the monomers for fluorine-containing resists of the product from polymerization. The polymerization inhibitor to be used is metoquinone, 2,5-di-t-butylhydroquinone, 1,2,4-trihydroxybenzene, 2,5-bistetramethylbutylhydroquinone, leucoquinazaline, nonplex F , Nonplex H, nonplex DCD, nonplex MBP, ozonone 35, phenothiazine, tetraethylthiuram disulfide, 1,1-diphenyl-2-picrylhydrazyl, 1,1-diphenyl-2 It is preferable that it is at least 1 sort (s) of compound chosen from -picrylhydrazine, Q-1300, Q-1301, 2-methoxyphenothiazine. The polymerization inhibitor can be easily obtained as a commercial item.

사용하는 중합 금지제의 양은 원료의

Figure pct00072
-치환 아크릴산 1몰에 대하여 0.00001∼0.1몰이고, 0.00005∼0.05몰이 바람직하고, 0.0001∼0.01몰이 보다 바람직하다. 중합 금지제의 양이 원료의
Figure pct00073
-치환 아크릴산 1몰에 대하여 0.1몰을 초과하여도 중합을 방지하는 능력에 큰 차이는 없고, 그 때문에 경제적으로 바람직하지 않다. 또한 중합 금지제의 양이 0.00001몰을 하회하면, 굳이 사용하는 효과가 얻어지기 어렵다.The amount of polymerization inhibitor to use
Figure pct00072
It is 0.00001-0.1 mol with respect to 1 mol of substituted acrylic acid, 0.00005-0.05 mol is preferable, and 0.0001-0.01 mol is more preferable. Amount of polymerization inhibitor
Figure pct00073
-Even if it exceeds 0.1 mol with respect to 1 mol of substituted acrylic acid, there is no big difference in the ability to prevent superposition | polymerization, and therefore it is economically unpreferable. Moreover, when the quantity of a polymerization inhibitor is less than 0.00001 mol, the effect of using daringly is hard to be acquired.

본 반응을 행하는 반응기는, 4불화에틸렌 수지, 클로로트리플루오로에틸렌 수지, 불화비닐리덴 수지, PFA 수지, 유리 등을 내부에 라이닝한 것, 글래스 용기, 혹은 스테인리스로 제작한 것이 바람직하다.As for the reactor which performs this reaction, what lined the inside with tetrafluoroethylene resin, chlorotrifluoroethylene resin, vinylidene fluoride resin, PFA resin, glass, etc. inside, glass container, or the thing made from stainless steel is preferable.

본 발명을 실시하는 방법은 한정되는 것은 아니지만, 바람직한 실시형태로는, 반응 조건에 견딜 수 있는 반응기에 촉매의 산 및, 용매, 원료의

Figure pct00074
-치환 아크릴산, 함불소알켄을 첨가하고, 외부로부터 가열하여 반응을 진행시키고, 샘플링 등에 의해 원료의 소비를 모니터링하여 반응이 종료된 것을 확인하고, 반응액을 냉각하는 것을 들 수 있다.The method of carrying out the present invention is not limited, but in a preferred embodiment, the acid, the solvent, and the raw material of the catalyst are placed in a reactor capable of withstanding the reaction conditions.
Figure pct00074
-Substituted acrylic acid and fluorine-alkene are added, the reaction is carried out by heating from the outside, and the consumption of raw materials is monitored by sampling or the like to confirm that the reaction is completed, and the reaction liquid can be cooled.

제조된 식 [3]의 함불소 레지스트용 모노머류는 공지된 방법을 적용하여 정제된다. 예를 들어, 물, 혹은 알칼리 수용액으로 반응액을 처리하고, 분액 조작에 의해 미반응의

Figure pct00075
-치환 아크릴산 및 사용한 산 촉매를 제거하고, 추가로 과잉의 함불소알켄을 증류 제거함으로써 조(粗)유기물이 얻어진다. 함불소알켄은 생성된 함불소 레지스트용 모노머류와 비점차가 커, 이배퍼레이터 등으로 용이하게 분리 가능하여, 과잉으로 사용하는 것에 의한 조작의 번잡함은 문제가 되지 않는다. 얻어진 조유기물은 칼럼 크로마토그래피나 증류 등의 정제를 행함으로써 고순도의 함불소 레지스트용 모노머류를 얻을 수 있다.The prepared monomers for the fluorine-containing resist of formula [3] are purified by applying a known method. For example, the reaction solution is treated with water or an aqueous alkali solution, and is separated from each other by the liquid separation operation.
Figure pct00075
Crude organics are obtained by removing substituted acrylic acid and the used acid catalyst and further distilling off excess fluorine alkene. The fluorine-alkene has a large difference in boiling point from the produced monomers for fluorine-containing resists, and can be easily separated by an evaporator, so that the troublesome operation by excessive use is not a problem. The obtained crude organic substance can obtain the monomers for fluorine-containing resists of high purity by refine | purifying, such as column chromatography and distillation.

반응 생성물인 식 [3]의 함불소 레지스트용 모노머류는 다음 식 [3a]와 [3b]로 나타내는 2개의 이성체의 혼합물로서 얻어진다.Monomers for fluorine-containing resists of formula [3] as reaction products are obtained as a mixture of two isomers represented by the following formulas [3a] and [3b].

[화학식 14][Formula 14]

Figure pct00076
Figure pct00076

이들 중에서 일방의 이성체만을 단리시키는 경우에는 칼럼 크로마토그래피 등의 방법에 따르면 된다. 단, 이성체의 단리를 행하지 않고, 이성체의 혼합물로서, 레지스트용의 모노머에 제공하는 것도 가능하다.In the case where only one isomer is isolated from these, methods such as column chromatography may be used. However, it is also possible to provide to the monomer for resists as a mixture of isomers, without isolating an isomer.

실시예Example

이하, 실시예에 의해 본 발명을 상세하게 설명하는데, 본 발명은 이들 실시예에 한정되지 않는다. 여기서, 조성 분석값의 「％」란, 반응 혼합물의 일부를 채취하여 물로 충분히 세정한 후, 유기 성분을 가스 크로마토그래피에 의해 측정하여 얻어진, 함불소알켄 성분을 제외한 유기 성분의 「면적％」를 나타낸다.EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these Examples. Here, "%" of the composition analysis value means that "area%" of the organic component except for the fluorine-alkene component obtained by collecting a part of the reaction mixture and sufficiently washing with water, and then measuring the organic component by gas chromatography. Indicates.

[실시예 1]Example 1

환류 냉각기를 상부에 장착한 1L의 3구 플라스크에 트리스(트리플루오로메탄술포닐)메탄을 3.5g(0.0085몰),

Figure pct00077
-트리플루오로메틸아크릴산을 100.0g(0.7몰), 1,1,1-트리플루오로-2-(트리플루오로메틸)펜타-4-엔-2-올을 594.3g(2.8몰) 넣고, 110℃의 오일 배스에 의해 가열하였다. 3시간 후, 조성을 가스 크로마토그래피에 의해 측정한 결과, 목적으로 하는 함불소 레지스트용 모노머류의 이성체 혼합물의 존재량(선택률)은 85.1％였다(선택률에 변환율 94.2％를 곱하여 산출되는, 겉보기 수율은 79.9％). 그 밖에 불순물로서, 원료의
Figure pct00078
-트리플루오로메틸아크릴산이 6.0％, 또한 생성물의 아크릴산 부위의 비닐기에 1분자의
Figure pct00079
-트리플루오로메틸아크릴산이 부가된 화합물(과부가체)이 1.1％ 검출되었다. 반응 결과(변환율, 선택률, 수량, 부생성물의 검출량 등)를 표 1에 나타낸다. 반응액을 냉각 후, 10％ 탄산나트륨(Na2CO3) 수용액 200g으로 세정한 후, 함불소알켄의 증류 제거를 행하고, 감압 증류(1.6ToRR=2kPa)하여, 80℃∼94℃의 유분(留分)을 모은 결과, 176g의 함불소 레지스트용 모노머류가 얻어졌다. 가스 크로마토그래피에 의해 조성을 조사한 결과, 목적물인 5,5,5-트리플루오로-4-하이드록시-4-(트리플루오로메틸)펜타-2-일(2-트리플루오로메틸)아크릴레이트의 이성체 혼합물의 순도는 98.5％, 그 밖의 불순물이 1.5％였다.3.5 g (0.0085 mol) tris (trifluoromethanesulfonyl) methane in a 1 L three-necked flask equipped with a reflux condenser on the top,
Figure pct00077
100.0 g (0.7 mol) of trifluoromethylacrylic acid, 594.3 g (2.8 mol) of 1,1,1-trifluoro-2- (trifluoromethyl) penta-4-en-2-ol, Heated by 110 ° C. oil bath. After 3 hours, the composition was measured by gas chromatography. As a result, the abundance (selectivity) of the isomer mixture of the target monomer for fluorine-containing resist was 85.1% (the apparent yield calculated by multiplying the conversion rate by 94.2%). 79.9%). As other impurities, raw materials
Figure pct00078
Trifluoromethylacrylic acid is 6.0%, and one molecule of the vinyl group
Figure pct00079
1.1% of compounds (hyperaddition) to which trifluoromethylacrylic acid was added were detected. Table 1 shows the reaction results (conversion rate, selectivity, yield, detection amount of by-products, etc.). After cooling, the reaction solution was washed with 200 g of 10% aqueous sodium carbonate (Na 2 CO 3 ) solution, and then distilled off fluorine-alkene, followed by distillation under reduced pressure (1.6 ToRR = 2 kPa) to obtain an oil of 80 ° C. to 94 ° C. As a result, 176 g of monomers for fluorine-containing resists were obtained. The composition was examined by gas chromatography. As a result, 5,5,5-trifluoro-4-hydroxy-4- (trifluoromethyl) penta-2-yl (2-trifluoromethyl) acrylate as a target product was examined. The purity of the isomer mixture was 98.5% and other impurities were 1.5%.

[실시예 2][Example 2]

환류 냉각기를 상부에 장착한 100mL의 3구 플라스크에 트리스(트리플루오로메탄술포닐)메탄을 0.8g(0.002몰),

Figure pct00080
-트리플루오로메틸아크릴산을 14.0g(0.1몰), 1,1,1-트리플루오로-2-(트리플루오로메틸)펜타-4-엔-2-올을 83.2g(0.4몰) 넣고, 110℃의 오일 배스에 의해 가열하였다. 8시간 후, 조성을 가스 크로마토그래피에 의해 측정한 결과, 목적으로 하는 함불소 레지스트용 모노머류의 이성체 혼합물의 존재량(선택률)은 89.1％였다(선택률에 변환율 93.9％를 곱하여 산출되는, 겉보기 수율은 83.7％). 그 밖에 불순물로서, 원료의
Figure pct00081
-트리플루오로메틸아크릴산이 6.2％, 또한 생성물의 아크릴산 부위의 비닐기에 1분자의
Figure pct00082
-트리플루오로메틸아크릴산이 부가된 화합물이 0.5％, 또한 동정(同定)할 수 없는 불순물이 합계로 9.5％ 검출되었다. 반응 결과(변환율, 선택률, 수량, 부생성물의 검출량 등)를 표 1에 나타낸다.0.8 g (0.002 mol) of tris (trifluoromethanesulfonyl) methane in a 100 mL three-necked flask equipped with a reflux condenser on the top,
Figure pct00080
14.0 g (0.1 mol) of trifluoromethylacrylic acid and 83.2 g (0.4 mol) of 1,1,1-trifluoro-2- (trifluoromethyl) penta-4-en-2-ol were added thereto. Heated by 110 ° C. oil bath. After 8 hours, as a result of measuring the composition by gas chromatography, the abundance (selectivity) of the isomeric mixture of the monomers for the fluorine-containing resist of interest was 89.1% (the apparent yield calculated by multiplying the selectivity by 93.9%). 83.7%). As other impurities, raw materials
Figure pct00081
Trifluoromethylacrylic acid is 6.2%, and one molecule of the vinyl group
Figure pct00082
0.5% of the compound to which trifluoromethylacrylic acid was added and 9.5% of impurities which could not be identified were detected in total. Table 1 shows the reaction results (conversion rate, selectivity, yield, detection amount of by-products, etc.).

[실시예 3]Example 3

환류 냉각기를 상부에 장착한 100mL의 3구 플라스크에 트리스(트리플루오로메탄술포닐)메탄을 0.29g(0.0007몰),

Figure pct00083
-트리플루오로메틸아크릴산을 14.0g(0.1몰), 1,1,1-트리플루오로-2-(트리플루오로메틸)펜타-4-엔-2-올을 41.6g(0.2몰) 넣고, 150℃의 오일 배스에 의해 가열하였다. 9시간 후, 조성을 가스 크로마토그래피에 의해 측정한 결과, 목적으로 하는 함불소 레지스트용 모노머류의 이성체 혼합물의 존재량(선택률)은 84.8％였다(선택률에 변환율 77.3％를 곱하여 산출되는, 겉보기 수율은 65.5％). 그 밖에 불순물로서, 원료의
Figure pct00084
-트리플루오로메틸아크릴산이 22.9％, 또한 생성물의 아크릴산 부위의 비닐기에 1분자의
Figure pct00085
-트리플루오로메틸아크릴산이 부가된 화합물이 2.2％, 또한 동정할 수 없는 불순물이 합계로 10％ 검출되었다. 반응 결과(변환율, 선택률, 수량, 부생성물의 검출량 등)를 표 1에 나타낸다.In a 100 mL three-necked flask equipped with a reflux condenser on the top, 0.29 g (0.0007 mol) of tris (trifluoromethanesulfonyl) methane,
Figure pct00083
14.0 g (0.1 mol) of trifluoromethylacrylic acid, 41.6 g (0.2 mol) of 1,1,1-trifluoro-2- (trifluoromethyl) penta-4-en-2-ol, Heated by 150 degreeC oil bath. After 9 hours, the composition was measured by gas chromatography. As a result, the abundance (selectivity) of the isomeric mixture of the target monomers for fluorine-containing resists was 84.8% (the apparent yield calculated by multiplying the selectivity by 77.3%). 65.5%). As other impurities, raw materials
Figure pct00084
Trifluoromethylacrylic acid is 22.9%, and one molecule of the vinyl group in the acrylic acid portion of the product
Figure pct00085
2.2% of the compounds to which -trifluoromethylacrylic acid was added and 10% of the impurities which cannot be identified were detected in total. Table 1 shows the reaction results (conversion rate, selectivity, yield, detection amount of by-products, etc.).

[실시예 4]Example 4

환류 냉각기를 상부에 장착한 100mL의 3구 플라스크에 트리스(트리플루오로메탄술포닐)메탄을 0.86g(0.002몰), 메타크릴산을 8.6g(0.1몰), 1,1,1-트리플루오로-2-(트리플루오로메틸)펜타-4-엔-2-올을 83.2g(0.4몰) 넣고, 110℃의 오일 배스에 의해 가열하였다. 7시간 후, 조성을 가스 크로마토그래피에 의해 측정한 결과, 목적으로 하는 함불소 레지스트용 모노머류의 이성체 혼합물의 존재량(선택률)은 89.0이었다(선택률에 변환율 78.9％를 곱하여 산출되는, 겉보기 수율은 70.3％). 그 밖에 불순물로서, 원료의 메타크릴산이 21.3％, 또한 생성물의 아크릴산 부위의 비닐기에 1분자의 메타크릴산이 부가된 화합물이 1.3％, 또한 동정할 수 없는 불순물이 합계로 8.1％ 검출되었다. 반응 결과(변환율, 선택률, 수량, 부생성물의 검출량 등)를 표 1에 나타낸다.In a 100 mL three-necked flask equipped with a reflux condenser on the top, 0.86 g (0.002 mol) of tris (trifluoromethanesulfonyl) methane, 8.6 g (0.1 mol) of methacrylic acid, 1,1,1-trifluoro 83.2 g (0.4 mol) of rho-2- (trifluoromethyl) penta-4-en-2-ols were put, and it heated by the 110 degreeC oil bath. After 7 hours, when the composition was measured by gas chromatography, the abundance (selectivity) of the isomer mixture of the monomers for the fluorine-containing resist of interest was 89.0 (the apparent yield calculated by multiplying the selectivity by 78.9% of the conversion rate was 70.3). %). In addition, as an impurity, 21.3% of methacrylic acid of the raw material, 1.3% of compounds in which one molecule of methacrylic acid was added to the vinyl group of the acrylic acid site of the product, and 8.1% of impurities which could not be identified were detected in total. Table 1 shows the reaction results (conversion rate, selectivity, yield, detection amount of by-products, etc.).

[실시예 5]Example 5

환류 냉각기를 상부에 장착한 100mL의 3구 플라스크에 트리스(트리플루오로메탄술포닐)메탄을 0.86g(0.002몰), 아크릴산을 7.2g(0.1몰), 1,1,1-트리플루오로-2-(트리플루오로메틸)펜타-4-엔-2-올을 83.2g(0.4몰) 넣고, 110℃의 오일 배스에 의해 가열하였다. 10시간 후, 조성을 가스 크로마토그래피에 의해 측정한 결과, 목적으로 하는 함불소 레지스트용 모노머류의 이성체 혼합물의 존재량(선택률)은 55.2％였다(선택률에 변환율 93.3％를 곱하여 산출되는, 겉보기 수율은 51.5％). 그 밖에 불순물로서, 원료의 아크릴산이 6.7％, 또한 생성물의 아크릴산 부위의 비닐기에 1분자의 메타크릴산이 부가된 화합물이 2.1％, 또한 동정할 수 없는 불순물이 합계로 39.7％ 검출되었다. 반응 결과(변환율, 선택률, 수량, 부생성물의 검출량 등)를 표 1에 나타낸다.In a 100 mL three-necked flask equipped with a reflux condenser on the top, 0.86 g (0.002 mol) of tris (trifluoromethanesulfonyl) methane, 7.2 g (0.1 mol) of acrylic acid, and 1,1,1-trifluoro- 83.2 g (0.4 mol) of 2- (trifluoromethyl) penta-4-en-2-ols were put, and it heated by the 110 degreeC oil bath. After 10 hours, the composition was measured by gas chromatography. As a result, the abundance (selectivity) of the isomeric mixture of the target monomers for fluorine-containing resists was 55.2% (the apparent yield calculated by multiplying the selectivity by 93.3%). 51.5%). In addition, as an impurity, 6.7% of the acrylic acid of the raw material, 2.1% of the compound in which one molecule of methacrylic acid was added to the vinyl group of the acrylic acid site of the product, and 39.7% of the unidentifiable impurities were detected in total. Table 1 shows the reaction results (conversion rate, selectivity, yield, detection amount of by-products, etc.).

[실시예 6]Example 6

환류 냉각기를 상부에 장착한 1L의 3구 플라스크에 트리플루오로메탄술폰산을 10.0g(0.07몰),

Figure pct00086
-트리플루오로메틸아크릴산을 100.0g(0.7몰), 1,1,1-트리플루오로-2-(트리플루오로메틸)펜타-4-엔-2-올을 594.3g(2.8몰) 넣고, 110℃의 오일 배스에 의해 가열하였다. 6시간 후, 조성을 가스 크로마토그래피에 의해 측정한 결과, 목적으로 하는 함불소 레지스트용 모노머류의 이성체 혼합물의 존재량(선택률)은 80.9％였다(선택률과 변환율 83.1％를 곱하여 산출되는, 겉보기 수율은 67.2％). 그 밖에 불순물로서, 원료의
Figure pct00087
-트리플루오로메틸아크릴산이 17.4％, 또한 생성물의 아크릴산 부위의 비닐기에 1분자의
Figure pct00088
-트리플루오로메틸아크릴산이 부가된 화합물(과부가체)이 7.7％, iso-BTHB가 1.9％ 검출되었다. 또한, 반응 후의 BTHB와 BTHB 이성체의 혼합비는, 약 1:2였다. 반응 결과(변환율, 선택률, 수량, 부생성물의 검출량 등)를 표 1에 나타낸다. 반응액을 냉각 후, 10％ 탄산나트륨(Na2CO3) 수용액 200g으로 세정한 후, 함불소알켄의 증류 제거를 행하고, 감압 증류(16ToRR=2kPa)하여, 80℃∼94℃의 유분을 모은 결과, 120g의 함불소 레지스트용 모노머류가 얻어졌다. 가스 크로마토그래피에 의해 조성을 조사한 결과, 목적물인 5,5,5-트리플루오로-4-하이드록시-4-(트리플루오로메틸)펜타-2-일(2-트리플루오로메틸)아크릴레이트의 이성체 혼합물의 순도는 98.5％, 그 밖의 불순물이 1.5％였다.10.0 g (0.07 mol) of trifluoromethanesulfonic acid in a 1 L three-necked flask equipped with a reflux condenser on the top,
Figure pct00086
100.0 g (0.7 mol) of trifluoromethylacrylic acid, 594.3 g (2.8 mol) of 1,1,1-trifluoro-2- (trifluoromethyl) penta-4-en-2-ol, Heated by 110 ° C. oil bath. After 6 hours, the composition was measured by gas chromatography. As a result, the abundance (selectivity) of the isomer mixture of the target monomer for fluorine-containing resists was 80.9% (the apparent yield calculated by multiplying the selectivity and the conversion rate 83.1%). 67.2%). As other impurities, raw materials
Figure pct00087
Trifluoromethylacrylic acid is 17.4%, and one molecule of the vinyl group in the acrylic acid portion of the product
Figure pct00088
7.7% and 1.9% of iso-BTHB were detected for the compound (hyperaddition) to which -trifluoromethylacrylic acid was added. In addition, the mixing ratio of BTHB and BTHB isomer after reaction was about 1: 2. Table 1 shows the reaction results (conversion rate, selectivity, yield, detection amount of by-products, etc.). After cooling the reaction solution, it was washed with 200 g of 10% aqueous sodium carbonate (Na 2 CO 3 ) solution, and then distilled off fluorine-alkene, followed by distillation under reduced pressure (16 ToRR = 2 kPa), and the oil content of 80 to 94 ° C was collected. And 120 g of monomers for fluorine-containing resists were obtained. The composition was examined by gas chromatography. As a result, 5,5,5-trifluoro-4-hydroxy-4- (trifluoromethyl) penta-2-yl (2-trifluoromethyl) acrylate as a target product was examined. The purity of the isomer mixture was 98.5% and other impurities were 1.5%.

[실시예 7]Example 7

환류 냉각기를 상부에 장착한 1L의 3구 플라스크에 트리플루오로메탄술폰산을 10.0g(0.07몰),

Figure pct00089
-트리플루오로메틸아크릴산을 100.0g(0.7몰), 1,1,1-트리플루오로-2-(트리플루오로메틸)펜타-4-엔-2-올을 297.15g(1.4몰) 넣고, 110℃의 오일 배스에 의해 가열하면서 1,1,1-트리플루오로-2-(트리플루오로메틸)펜타-4-엔-2-올을 297.15g(1.4몰)을 6시간에 걸쳐 적하하였다. 적하 개시로부터 8시간 후, 조성을 가스 크로마토그래피에 의해 측정한 결과, 목적으로 하는 함불소 레지스트용 모노머류의 이성체 혼합물의 존재량(선택률)은 75.3％였다(선택률과 변환율 82.2％를 곱하여 산출되는, 겉보기 수율은 61.9％). 반응 결과(변환율, 선택률, 수량, 부생성물의 검출량 등)를 표 1에 나타낸다.10.0 g (0.07 mol) of trifluoromethanesulfonic acid in a 1 L three-necked flask equipped with a reflux condenser on the top,
Figure pct00089
100.0 g (0.7 mol) of trifluoromethylacrylic acid, 297.15 g (1.4 mol) of 1,1,1-trifluoro-2- (trifluoromethyl) penta-4-en-2-ol, 297.15 g (1.4 mol) of 1,1,1-trifluoro-2- (trifluoromethyl) penta-4-en-2-ol was dripped over 6 hours, heating by the 110 degreeC oil bath. . After 8 hours from the start of dropwise addition, the composition was measured by gas chromatography. As a result, the abundance (selectivity) of the isomer mixture of the target monomers for fluorine-containing resists was 75.3% (calculated by multiplying the selectivity and the conversion rate 82.2%, Apparent yield 61.9%). Table 1 shows the reaction results (conversion rate, selectivity, yield, detection amount of by-products, etc.).

[실시예 8]Example 8

환류 냉각기를 상부에 장착한 1L의 3구 플라스크에 트리플루오로메탄술폰산을 10g(0.07몰),

Figure pct00090
-트리플루오로메틸아크릴산을 100.0g(0.7몰), 1,1,1-트리플루오로-2-(트리플루오로메틸)펜타-4-엔-2-올을 436.8g(2.1몰) 넣고, 110℃의 오일 배스에 의해 가열하였다. 6시간 후, 조성을 가스 크로마토그래피에 의해 측정한 결과, 목적으로 하는 함불소 레지스트용 모노머류의 이성체 혼합물의 존재량(선택률)은 68.8％였다(선택률과 변환율 81.0％를 곱하여 산출되는, 겉보기 수율은 55.7％). 반응 결과(변환율, 선택률, 수량, 부생성물의 검출량 등)를 표 1에 나타낸다.10 g (0.07 mol) of trifluoromethanesulfonic acid in a 1 L three-necked flask equipped with a reflux condenser on the top,
Figure pct00090
100.0 g (0.7 mol) of trifluoromethylacrylic acid, 436.8 g (2.1 mol) of 1,1,1-trifluoro-2- (trifluoromethyl) penta-4-en-2-ol, Heated by 110 ° C. oil bath. After 6 hours, when the composition was measured by gas chromatography, the abundance (selectivity) of the isomeric mixture of the target monomers for fluorine-containing resists was 68.8% (the apparent yield calculated by multiplying the selectivity and the conversion rate 81.0%). 55.7%). Table 1 shows the reaction results (conversion rate, selectivity, yield, detection amount of by-products, etc.).

[실시예 9]Example 9

환류 냉각기를 상부에 장착한 1L의 3구 플라스크에 황산을 9.8g(0.1몰),

Figure pct00091
-트리플루오로메틸아크릴산을 100.0g(0.7몰), 1,1,1-트리플루오로-2-(트리플루오로메틸)펜타-4-엔-2-올을 594.3g(2.8몰) 넣고, 120℃의 오일 배스에 의해 가열하였다. 7시간 후, 조성을 가스 크로마토그래피에 의해 측정한 결과, 목적으로 하는 함불소 레지스트용 모노머류의 이성체 혼합물의 존재량(선택률)은 65.3％였다(선택률과 변환율 63.1％를 곱하여 산출되는, 겉보기 수율은 41.2％). 반응 결과(변환율, 선택률, 수량, 부생성물의 검출량 등)를 표 1에 나타냈다.9.8 g (0.1 mol) of sulfuric acid in a 1 L three-necked flask equipped with a reflux condenser on the top,
Figure pct00091
100.0 g (0.7 mol) of trifluoromethylacrylic acid, 594.3 g (2.8 mol) of 1,1,1-trifluoro-2- (trifluoromethyl) penta-4-en-2-ol, Heated by an oil bath at 120 ° C. After 7 hours, when the composition was measured by gas chromatography, the abundance (selectivity) of the isomer mixture of the monomers for the fluorine-containing resist of interest was 65.3% (the apparent yield calculated by multiplying the selectivity by 63.1% conversion) 41.2%). Table 1 shows the reaction results (conversion rate, selectivity, yield, detection amount of by-products, etc.).

[비교예 1∼5]Comparative Examples 1 to 5

환류 냉각기를 상부에 장착한 100mL의 2구 플라스크에

Figure pct00092
-치환 아크릴산을 10g, 1,1,1-트리플루오로-2-(트리플루오로메틸)펜타-4-엔-2-올을
Figure pct00093
-치환 아크릴산에 대하여 임의의 몰수 넣고, 산 촉매(
Figure pct00094
-치환 아크릴산에 대하여 10wt％)의 종류를 바꾸어, 임의의 온도에서 실시예 1과 동일한 반응을 행하였다. 사용한 산 촉매는, 메탄술폰산, p-톨루엔술폰산, 캠퍼술폰산, 비스(트리플루오로메탄술포닐)메탄, 1,1,1-트리플루오로-N-(트리플루오로메탄술포닐)메탄술폰아미드로, 각각 비교예 1∼5로 하였다. 반응 종료 후, 조성을 가스 크로마토그래피에 의해 측정하였다. 그 결과를 표 1에 나타낸다.Into a 100 mL two-necked flask equipped with a reflux condenser on top.
Figure pct00092
10 g of substituted acrylic acid, 1,1,1-trifluoro-2- (trifluoromethyl) penta-4-en-2-ol
Figure pct00093
-Arbitrary mole number with respect to substituted acrylic acid, and acid catalyst (
Figure pct00094
-10 wt%) was changed with respect to substituted acrylic acid, and reaction similar to Example 1 was performed at arbitrary temperature. Acid catalysts used were methanesulfonic acid, p-toluenesulfonic acid, camphorsulfonic acid, bis (trifluoromethanesulfonyl) methane, 1,1,1-trifluoro-N- (trifluoromethanesulfonyl) methanesulfonamide In each case, Comparative Examples 1 to 5 were used. After the completion of the reaction, the composition was measured by gas chromatography. The results are shown in Table 1.

[참고예] 산 촉매 존재 하에서의 BTHB의 이성화Reference Example Isomerization of BTHB in the Presence of Acid Catalysts

환류 냉각기를 상부에 장착한 50mL의 3구 플라스크에 산 촉매로서 트리플루오로메탄술폰산을 9.8g(0.1몰), 함불소올레핀으로서 1,1,1-트리플루오로-2-(트리플루오로메틸)펜타-4-엔-2-올(BTHB)을 29.7g(0.14몰) 넣고, 100℃의 오일 배스에 의해 가열하였다. 19시간 후, 조성을 가스 크로마토그래피에 의해 측정한 결과, BTHB와 BTHB 이성체의 비는 8:92였다.In a 50 mL three-necked flask equipped with a reflux condenser on the top, 9.8 g (0.1 mol) of trifluoromethanesulfonic acid as an acid catalyst, and 1,1,1-trifluoro-2- (trifluoromethyl) as a fluorine-containing olefin. ) 29.7 g (0.14 mol) of penta-4-en-2-ol (BTHB) was put, and it heated by the oil bath of 100 degreeC. After 19 hours, the composition was measured by gas chromatography, and the ratio of the BTHB and BTHB isomers was 8:92.

Figure pct00095
Figure pct00095

표 1로부터, 트리플루오로메틸아크릴산과 BTHB의 반응계에 있어서 트리스(트리플루오로메탄술포닐)메탄을 산 촉매로서 사용한 경우(실시예 1∼3)에는, iso-체의 생성 및 과부가체의 생성이 억제되고, 게다가, 목적물이 높은 수율로 얻어지는 것을 알 수 있었다. 또한, 트리플루오로메틸아크릴산과 BTHB의 반응계에 있어서 산 촉매로서 트리플루오로메탄술폰산을 사용한 경우(실시예 6∼8)에는, 이성체 및 과부가체는 생성되지만 디올체의 생성은 억제되어, 목적물이 비교적 양호한 수율로 얻어지는 것을 알 수 있었다. 트리플루오로메틸아크릴산과 BTHB의 반응계에 있어서 산 촉매로서 황산을 사용한 경우(실시예 9)에는, 디올체는 생성되지만, 이성체 및 과부가체의 생성이 억제되어, 목적물이 얻어지는 것을 알 수 있었다. 한편, 트리플루오로메틸아크릴산과 BTHB의 반응계에서, 산 촉매로서 pKa가 높은 산을 사용한 경우(비교예 1∼5)에는, 반응이 진행되지 않았다.From Table 1, when tris (trifluoromethanesulfonyl) methane was used as the acid catalyst in the reaction system of trifluoromethylacrylic acid and BTHB (Examples 1 to 3), the formation of iso-forms and the formation of hyperadditions This was suppressed and it turned out that the target object is obtained in a high yield. In addition, when trifluoromethanesulfonic acid is used as an acid catalyst in the reaction system of trifluoromethylacrylic acid and BTHB (Examples 6 to 8), isomers and hyperadditions are produced, but formation of diols is suppressed. It turned out that it is obtained with a relatively good yield. When sulfuric acid was used as the acid catalyst in the reaction system of trifluoromethylacrylic acid and BTHB (Example 9), the diol was produced, but the formation of isomers and hyperaddition was suppressed, and it was found that the target product was obtained. On the other hand, in the reaction system of trifluoromethyl acrylic acid and BTHB, when an acid having high pKa was used as the acid catalyst (Comparative Examples 1 to 5), the reaction did not proceed.

상기 서술한 바와 같이, 본 발명의 제조 방법에서는, 술포닐기를 가지는 특정한 산 촉매 존재 하에서,

Figure pct00096
-치환 아크릴산을 함불소알켄에 직접 부가 반응시켜,
Figure pct00097
-치환 아크릴산 에스테르계의 함불소 레지스트용 모노머류를 제조한다. 알켄의 이성화, 디올체의 생성, 아크릴산의 과부가 반응이 부반응으로서 진행되는 가운데, 목적으로 하는 부가 반응을 효율적으로 진행시킬 수 있기 때문에, 공업적 규모에서의
Figure pct00098
-치환 아크릴산 에스테르계의 함불소 레지스트용 모노머류의 제조를 가능하게 한다.As described above, in the production method of the present invention, in the presence of a specific acid catalyst having a sulfonyl group,
Figure pct00096
-By directly adding the substituted acrylic acid to the fluorine-alkene,
Figure pct00097
-Substituted acrylic ester monomers for fluorine-containing resists are prepared. While the isomerization of alkenes, the formation of diols, and the addition reaction of acrylic acid proceed as side reactions, the target addition reaction can be efficiently carried out.
Figure pct00098
-It is possible to manufacture monomers for fluorine-containing resists of substituted acrylic acid esters.

본 발명을 구체적인 실시예에 기초하여 설명하였으나, 본 발명은 상기 실시예에 한정되는 것은 아니며, 그 취지를 일탈하지 않는 범위에서 다양한 변형·변경을 포함하는 것이다.Although this invention was demonstrated based on the specific Example, this invention is not limited to the said Example, Comprising: Various deformation | transformation and a change are included in the range which does not deviate from the meaning.

Claims (4)

식 [1]로 나타내는 함불소알켄과 식 [2]로 나타내는
Figure pct00099
-치환 아크릴산을 산 촉매의 존재 하에서 반응시키는, 식 [3]으로 나타내는 함불소 레지스트용 모노머류의 제조 방법에 있어서, 해당 산 촉매가 식 [4]로 나타내는 술포닐기를 가지는 산인, 함불소 레지스트용 모노머류의 제조 방법.
[화학식 15]
Figure pct00100

[화학식 16]
Figure pct00101

[R1은 수소 원자, 불소 원자 또는 탄소수 1∼6의 직쇄 혹은 분기쇄가 있는 알킬기를 나타내고, 당해 알킬기의 일부 또는 전부가 불소 원자에 의해 치환되어 있어도 된다.]
[화학식 17]
Figure pct00102

[R1은 식 [1]과 동일하다.]
[화학식 18]
Figure pct00103

[A는 산소 원자 또는 탄소 원자를 나타내고, Rf는 서로 각각 독립적으로 동일하거나 다른 불소 원자, 하이드록실기 또는 탄소수 1∼6의 함불소알킬기를 나타내며, n은 1 또는 3의 정수를 나타낸다.]Fluorinated alkene represented by Formula [1] and represented by Formula [2]
Figure pct00099
-In the manufacturing method of the monomer for fluorine-containing resist represented by Formula [3] which reacts substituted acrylic acid in presence of an acid catalyst, the acid catalyst is an acid which has a sulfonyl group represented by Formula [4], for a fluorine-containing resist. The manufacturing method of monomers.
[Formula 15]
Figure pct00100

[Formula 16]
Figure pct00101

[R 1 represents a hydrogen atom, a fluorine atom or a linear or branched alkyl group having 1 to 6 carbon atoms, and part or all of the alkyl group may be substituted with a fluorine atom.]
[Chemical Formula 17]
Figure pct00102

[R 1 is the same as Equation [1].
[Chemical Formula 18]
Figure pct00103

[A represents an oxygen atom or a carbon atom, R f each independently represents the same or different fluorine atom, hydroxyl group or C1-6 fluorine-containing alkyl group, n represents an integer of 1 or 3.] 제1항에 있어서,
산 촉매의 pKa가 -5 이하인, 함불소 레지스트용 모노머류의 제조 방법.The method of claim 1,
The manufacturing method of the monomers for fluorine-containing resists whose pKa of an acid catalyst is -5 or less. 제1항 또는 제2항에 있어서,
반응 온도가 30℃ 내지 200℃인, 함불소 레지스트용 모노머류의 제조 방법.The method according to claim 1 or 2,
The manufacturing method of the monomers for fluorine-containing resists whose reaction temperature is 30 degreeC-200 degreeC. 제1항 내지 제3항 중 어느 한 항에 있어서,
식 [2]로 나타내는
Figure pct00104
-치환 아크릴산 1몰에 대하여, 식 [1]로 나타내는 함불소알켄의 사용량이 2∼10몰인, 함불소 레지스트용 모노머류의 제조 방법.4. The method according to any one of claims 1 to 3,
Represented by formula [2]
Figure pct00104
-The manufacturing method of the monomer for fluorine-containing resists whose usage-amount of the fluorine-alkene represented by Formula [1] is 2-10 mol with respect to 1 mol of substituted acrylic acid.
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Family Cites Families (21)

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Publication number Priority date Publication date Assignee Title
JPS5921648A (en) 1982-07-29 1984-02-03 Sagami Chem Res Center Methacrylic acid ester containing fluorine
DE3913781A1 (en) * 1989-04-26 1990-10-31 Hoechst Ag METHOD FOR PRODUCING NITRO-BENZOESIC ACID ALKYL ESTERS
JP3049578B2 (en) 1991-12-06 2000-06-05 東ソー株式会社 Method for producing alkadienols
DE19743985A1 (en) * 1997-10-06 1999-04-08 Merck Patent Gmbh New tris:tri:fluoromethyl-sulfonyl-methane and its salts used as catalysts e.g., in cycloaddition reactions
DE19835358A1 (en) * 1998-08-05 2000-02-10 Clariant Gmbh Synthesis of o- (p-tolyl) benzoic acid tert-butyl ester by reacting o- (p-tolyl) benzoic acid with isobutylene with acid catalysis
JP4083399B2 (en) 2001-07-24 2008-04-30 セントラル硝子株式会社 Fluorine-containing polymerizable monomer and polymer compound using the same
ATE532764T1 (en) * 2001-12-14 2011-11-15 Dsm Ip Assets Bv PRODUCTION OF TRIMETHYLHYDROCHINONDIACYLATES
EP1490457B1 (en) * 2002-04-01 2007-06-13 E.I. du Pont de Nemours and Company Preparation of levulinic acid esters and formic acid esters from biomass and olefins
US6806026B2 (en) * 2002-05-31 2004-10-19 International Business Machines Corporation Photoresist composition
JP2004175740A (en) * 2002-11-28 2004-06-24 Central Glass Co Ltd METHOD FOR PRODUCING alpha-SUBSTITUTED ACRYLIC ACID NORBORNANYLS
JP3797618B2 (en) * 2003-02-20 2006-07-19 独立行政法人科学技術振興機構 Method for producing chroman compound derivative
JP4557502B2 (en) 2003-02-21 2010-10-06 セントラル硝子株式会社 Fluorine-based cyclic compound, fluorine-based polymerizable monomer, fluorine-based polymer compound, and resist material and pattern forming method using the same
JP2005060337A (en) * 2003-08-19 2005-03-10 National Institute Of Advanced Industrial & Technology Method for producing aromatic ketone and catalyst for producing the same
CN1874988B (en) * 2003-11-07 2010-09-08 帝斯曼知识产权资产管理有限公司 Process for the preparation of 2,3,5-trimethylhydroquinone diacylates
JP4632759B2 (en) 2003-11-26 2011-02-16 セントラル硝子株式会社 Method for producing α-substituted norbornanyl acrylates
JP4667035B2 (en) * 2003-12-26 2011-04-06 セントラル硝子株式会社 Process for producing 1,1-bis (trifluoromethyl) -1,3-diols acrylic ester
JP4324569B2 (en) * 2004-01-27 2009-09-02 セントラル硝子株式会社 Process for producing fluorine-containing 2,4-diols and derivatives thereof
US7205443B2 (en) 2004-01-27 2007-04-17 Central Glass Company, Limited Processes for producing fluorine-containing 2,4-diols and their derivatives
FR2889519B1 (en) * 2005-08-04 2008-07-11 Rhodia Chimie Sa PROCESS FOR C-ALKYLATION OF HYDROXYLIC AROMATIC COMPOUNDS WITH A TFSIH-TYPE CATALYST
JP4887710B2 (en) * 2005-09-28 2012-02-29 セントラル硝子株式会社 Method for producing α-substituted norbornanyl acrylates
JP5223305B2 (en) * 2007-07-31 2013-06-26 ダイキン工業株式会社 Method for producing fluorine-containing keto alcohol and derivatives thereof

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US20120004444A1 (en) 2012-01-05
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US8524941B2 (en) 2013-09-03
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